Process for hydroformylation of unsaturated compounds using iron carbonyl catalysts

ABSTRACT

The invention is a process for the hydroformylation of C 2-4  alkenes, formyl-substituted C 2-4  alkenes, aryl-substituted alkenes, unsaturated norbornane ring-containing compounds, and α-unsaturated acetals which comprises contacting a C 2-4  alkene, a formyl-substituted C 2-4  alkene, aryl-substituted alkene, an unsaturated norbornane ring-containing compound or an α-unsaturated acetal in a polar organic solvent with water and carbon monoxide in the presence of a catalytic amount of a catalyst which comprises a mixture of (a) an alkali metal iron carbonyl or alkaline earth metal iron carbonyl which corresponds to the formula M a  Fe x  (CO) y  and (b) iron pentacarbonyl under conditions such that an alcohol or aldehyde derivative of a C 2-4  alkene, a formyl-substituted C 2-4  alkene, an aryl-substituted alkene, unsaturated norbornane ring-containing compound or an α-unsaturated acetal, is prepared wherein M is an alkali metal or alkaline earth metal; a is 1 or 2; x is an integer of 2 to 4, inclusive; and y is 8, 11 or 13.

BACKGROUND OF THE INVENTION

This invention relates to a novel process for the hydroformylation ofcertain unsaturated compounds. More specifically, it relates to the useof certain iron carbonyl catalysts.

The hydroformylation of olefins with hydrogen and carbon monoxide is awell-known process. Most known processes require the use of rhodium orcobalt in various forms as catalysts. These processes are generally runat elevated temperatures and pressures, for example, about 125° C. to175° C. and about 3000 to 5000 psig. Cobalt- and rhodium-based catalystsare expensive and often render processes using them uneconomical.Furthermore, many of these catalysts require stringent conditions inorder to be operable.

As a result of these problems many researchers have attempted to useother catalyst systems for hydroformylation of olefins. An olefin can beconverted to the next higher alcohol by reaction with water and carbonmonoxide in the presence of a catalyst comprising a Bronsted or Lewisbase and iron pentacarbonyl under relatively mild temperatures andpressures. W. Reppe et al., Justus Liebigs Ann. Chem., 582 133 (1953).Kang et al., J. Am. Chem. Soc., 99 8323 (1977), disclose that thepresence of a strong base is necessary for iron pentacarbonyl to becatalytic in he Reppe synthesis. In hydroformylation reactions, carbondioxide is a by-product which reacts with the base to deactivate thecatalytic system. Such side reactions result in significant reductionsin the number of times the catalyst can be regenerated. As a result,these processes requre large amounts of base for the catalyst tocontinue its catalytic activity.

What is needed is a catalyst system for hydroformylation of olefinswhich does not contain expensive metals such as cobalt or rhodium andwhich requires mild reaction conditions. What is further needed is aprocess which retains its catalytic activity for extended periods oftime without the use of large amounts of base.

SUMMARY OF THE INVENTION

The invention is a process for the hydroformylation of C₂₋₄ alkenes,unsaturated norbornane ring-containing compounds, and α-unsaturatedacetals which comprises contacting a C₂₋₄ alkene, a formyl-substitutedC₂₋₄ alkene, an aryl-substituted alkene, an unsaturated norbornanering-containing compound or an α-unsaturated acetal in a polar organicsolvent with water and carbon monoxide in the presence of a catalyticamount of a catalyst which comprises a mixture of (a) an alkali metalcarbonyl, alkaline metal carbonyl or a mixture thereof which correspondsto the formula M_(a) [Fe_(x) (CO)_(y) ] and (b) iron pentacarbonyl underconditions such that an alcohol or aldehyde derivative of a C₂₋₄ alkene,C₂₋₄ formyl-substituted alkene, an aryl-substituted alkene, anα-unsaturated norbornane ring-containing compound, or an α-unsaturatedacetal is prepared, wherein M is an alkali metal or alkaline earthmetal; a is the integer 1 or 2; x is an integer of from 2 to 4inclusive; and y is the integer 8, 11 or 13.

In another aspect the invention is a hydroformylation catalyst whichcomprises (a) an iron carbonyl compound which corresponds to the formulaM_(a) [Fe_(x) (CO)_(y) ] and (b) iron pentacarbonyl wherein M, x and yare as defined hereinbefore.

The novel catalyst of this invention does not require the presence oflarge amounts of base to retain its catalytic activity for extendedperiods of use. The reaction conditions require for catalytic activityare relatively mild. Furthermore, these iron-based catalysts are lessexpensive than the cobalt- and rhodium-containing catalysts of the priorart.

DETAILED DESCRIPTION OF THE INVENTION

The novel hydroformylation catalysts of this invention have catalyticactivity for only selected olefins. These olefins are C₂₋₄ alkenes, aformyl-substituted C₂₋₄ alkene, an aryl-substituted alkene, unsaturatednorbornane ring-containing compounds, and α-unsaturated acetals.

The C₂₋₄ alkenes, formyl-substituted C₂₋₄ alkenes and aryl-substitutedalkenes useful in this invention include those corresponding to theformula

    (R.sup.1).sub.2 --C═C--(R.sup.1).sub.2

wherein R¹ is separately in each occurrence hydrogen, methyl, ethyl, aformyl group, a phenyl group, or a phenyl group substituted with analkyl, aryl, formyl, halo, nitro, cyano, alkoxy or aryloxy group.Examples of alkenes useful in this invention include ethylene,propylene, 1-butene, 2-butene, styrene, 2-propenal and 2-butenal.

The unsaturated norbornane ring-containing compounds include anycompounds which contain a norbornane ring in which the norbornane ringcontains unsaturation. Included among such compounds are those whichcorrespond to the formulas ##STR1## wherein R² is separately in eachoccurrence hydrogen, a hydroxymethyl, a formyl group or a C₁₋₂₀hydrocarbyl group. R² is preferably hydrogen, a formyl or C₁₋₁₀ alkylgroup, even more preferably hydrogen, a formyl or C₁₋₃ alkyl group, andmost preferably hydrogen or a formyl group. Examples of compounds usefulin this invention include norbornene, norbornene carboxaldehyde,norbornanediene and dicyclopentadiene.

The α-unsaturated acetals include compounds which contain an acetalfunctionality and unsaturation on the carbon atom α to the acetal carbonatom. Such compounds which are useful in this invention include thosewhich correspond to the formula ##STR2## wherein R³ is separately ineach occurrence hydrogen or C₁₋₂₀ alkyl; R⁴ is hydrogen or methyl; andR⁵ is separately in each occurrence a C₁₋₂₀ hydrocarbyl group, or the R⁵'s may combine to form a cyclic acetal ring.

R³ is preferably hydrogen or C₁₋₂₀ alkyl, more preferably hydrogen orC₁₋₃ alkyl, even more preferably hydrogen or methyl and most preferablyhydrogen.

R⁵ is preferably C₁₋₂₀ alkyl, more preferably C₁₋₃ alkyl, and mostpreferably methyl or ethyl. Examples of compounds useful in this processinclude 3,3-dimethoxy-1-propene; 3,3-diethoxy-1-propene; and3,3-dimethoxy-2-methyl-1-propene.

In general, the products of this invention are aldehyde-(formyl) oralcohol-(phydroxymethyl) substituted derivatives, or mixtures thereof,of the olefins described hereinbefore. Specifically, either a formyl orhydroxymethyl moiety is inserted at the point of unsaturation.

When the olefin is a C₂₋₄ alkene, the product is a C₃₋₅ alkanol, a C₃₋₅alkanal or mixtures thereof. When the olefin is a formyl-substitutedC₂₋₄ alkene, the product is a C₃₋₅ alkanediol, a C₃₋₅ alkanedial or amixture thereof. Under the conditions wherein an alcohol moiety isadded, the formyl moiety undergoes hydrogenation to prepare an alcoholmoiety. When the olefin is an aryl-substituted alkene, the product is anaryl-substituted alkanal, an aryl-substituted alcohol or a mixturethereof. The C₃₋₅ alkanols, C₃₋₅ alkanediols and aryl-substitutedalcohols correspond to the formula ##STR3## and the C₃₋₅ alkanals, C₃₋₅alkanedials and aryl-substituted alkanals correspond to the formulawherein R¹ is as defined hereinbefore.

Examples of alcohols prepared by this process include propanol, butanoland pentanol. Examples of alkanals prepared include propanal, butanal orpentanal.

The process conditions can be adjusted to give the desired product mix,that is, alkanols, alkanals, or a particular mixture thereof. Inparticular, the reaction temperature is critical to the product mix.Alkanols are the preferred products. In those embodiments wherein thealkene contains unsaturation on a terminal carbon atom, the process ofthis invention prepares primarily straight-chained alkanols andalkanals.

In the embodiment wherein an unsaturated norbornane ring-containingcompound is the olefin, the products of the invented process areformyl-substituted norbornane ring-containing compounds,hydroxymethyl-substituted norbornane ring-containing compounds, ormixtures thereof. The hydroxymethyl-substituted norbornanering-containing compounds include those corresponding to the formula##STR4## and the formyl-substituted norbornane ring-containing compoundcorresponds to the formula ##STR5## wherein R² is as definedhereinbefore. Examples of compounds prepared by this process includenorbornane carboxaldehyde, norbornane methanol, norbornanedicarboxaldehyde and norbornane dimethanol. The preferred products ofthe process of this invention are the hydroxymethyl-substitutedcompounds.

In the embodiment wherein the unsaturated norbornane ring-containingcompound is dicyclopentadiene, the process of this invention selectivelyhydroformylates the unsaturated point on the norbornane ring withouthydroformylating the unsaturation of the other ring.

In the embodiment wherein the unsaturated norbornane ring-containingcompound is substituted with a formyl moiety, under those conditionswherein the hydroxymethyl-substituted compound is prepared, the formylmoiety undergoes hydrogenation to prepare a second hydroxymethyl moiety.

In the embodiment where an α-unsaturated acetal is the olefin, theproducts are generally formyl-substituted acetals,hydroxymethyl-substituted acetals or mixtures thereof. Theformyl-substituted acetals generally correspond to the formulas ##STR6##and the hydroxymethyl-substituted acetal corresponds to the formula##STR7## wherein R³, R⁴ and R⁵ are as defined hereinbefore.

Examples of such products include 4,4-dimethoxybutanal,4,4-diethoxybutanal, 4,4-dimethoxybutanol and 4,4-diethoxybutanol. Inthe embodiment wherein R³ is hydrogen, the substitution on theα-unsaturated acetal occurs primarily on the β carbon atom. Thehydroxymethyl acetal is the preferred product of this process.

Formyl refers herein to a carboxaldehyde moiety which corresponds to theformula ##STR8##

Hydrocarbyl means herein an organic radical containing carbon andhydrogen atoms. The term hydrocarbyl includes the following organicradicals: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl,aliphatic and cycloaliphatic aralkyl and alkaryl. Aliphatic refersherein to straight- and branched-, and saturated and unsaturated,hydrocarbon chains, that is, alkyl, alkenyl or alkynyl. Cycloaliphaticrefers herein to saturated and unsaturated cyclic hydrocarbons, that is,cycloalkenyl and cycloalkyl. The term aryl refers herein to biaryl,biphenylyl, phenyl, naphthyl, phenanthranyl, anthranyl and two arylgroups bridged by an alkylene group. Alkaryl refers herein to an alkyl-,alkenyl- or alkynyl-substituted aryl substituent wherein aryl is asdefined hereinbefore. Aralkyl means herein an alkyl, alkenyl or alkynylgroup substituted with an aryl group, wherein aryl is as definedhereinbefore. C₁₋₂₀ alkyl includes straight- and branched-chain methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl and eicosyl groups. C₁₋₅ alkyl includesmethyl, ethyl, propyl, butyl and pentyl.

Cycloalkyl refers to alkyl groups containing one, two, three or morecyclic rings. Cycloalkenyl refers to mono-, di- and polycyclic groupscontaining one or more double bonds. Cycloalkenyl also refers tocycloalkenyl groups wherein two or more double bonds are present.

The novel catalyst of this invention comprises a mixture of (a) analkali metal iron carbonyl or an alkaline earth metal iron carbonylcompound which corresponds to the formula M_(a) [Fe_(x) (CO)_(y) ], and(b) an iron pentacarbonyl wherein M is an alkali metal or alkaline earthmetal; a is 1 or 2; x is 2, 3 or 4; and y is 8, 11 or 13. Preferredalkali metal iron carbonyl or alkaline earth metal iron carbonylcompounds include M₂ Fe₂ (CO)₈, M₂ Fe₃ (CO)₁₁ and M₂ Fe₄ (CO)₁₃.Preferably, x is 2 and y is 8. Wherein M is an alkali metal cation, a is2, and wherein M is an alkaline earth metal, a is 1. Alkali metal refersherein to lithium, sodium, potassium, rubidium and cesium. Alkalineearth metal refers herein to beryllium, magnesium, calcium, strontium orbarium. M is preferably an alkali metal, more preferably potassium,sodium or lithium, and most preferably potassium.

The relative ratio of the catalyst components can be any ratio whichprovides a catalyst which effectively catalyzes the reaction.Preferably, the molar ratio of the iron pentacarbonyl to the alkalimetal or alkaline earth metal iron carbonyl compound is between about0.01:1.0 to 10:1 and more preferably between 1.0:1.0 and 10.0:1.0.

The catalyst is prepared by dissolving an iron nonacarbonyl compoundwhich corresponds to the formula Fe_(x) (CO)_(z) in a suitable solventwhich contains at least an equivalent amount of an alkali metal base oralkaline earth metal base (hydroxide and the like) to prepare the alkalimetal iron carbonyl or alkaline earth metal iron carbonyl compound. Tothis solution is added iron pentacarbonyl.

A catalytic amount of the catalyst composition is that amount whichcatalyzes the reaction. Preferably, a catalytic amount of the catalystis between about 0.1 and 30 mole percent based upon the olefin and morepreferably between about 1 and 10 mole percent.

The hereinbefore olefins are reacted with carbon monoxide and waterunder conditions such that a formyl or hydroxymethyl group is insertedat the point of unsaturation. In general, to get complete conversions,at least a stoichiometric amount of carbon monoxide and water isrequired. It is advantageous to use an excess of carbon monoxide and insome embodiments the reactor is pressurized with excess carbon monoxide.If too much water is used, unwanted by-products are formed. The amountof water used is that amount which is sufficient to provide the desiredconversion and which does not result in the formation of unwantedby-products. Preferably, between about 1 and 5 moles of water per moleof olefin is used, most preferably between about 1 and 3.

It is believed that this reaction proceeds by a two-step sequence. Inthe first step a formyl group is inserted on the double bond. In thesecond step, the formyl group is hydrogenated to a hydroxymethyl group.By controlling the reaction conditions, the relative amounts of formyl-and hydroxymethyl-substituted products can be controlled.

In general, the olefin is dissolved in a polar organic solvent,contacted with the catalyst and exposed to reaction conditions. Thecatalyst can be added to the solvent after addition of the olfein or thecatalyst may be present in the solvent when the olefin is added.

The temperatures suitable for this reaction are those at which thereaction proceeds. Preferable temperatures are between 80° C. and 140°C. At temperatures below 80° C., the reaction rate is slow. Attemperatures above 140° C., the formation of undesirable by-productstakes place. At temperatures below 120° C., hydrogenation is very slow,whereas above 120° C., the formyl group undergoes hydrogenation to thehydroxymethyl group. As the temperature is increased, the overallconversion increases.

The reaction is pH sensitive. It is preferable to run the reaction at apH of greater than 6, more preferable at a pH of 6 to 9, with a pH of 6to 8 being most preferable. A neutral pH gives the optimum results.Below a pH of 6, the reaction does not proceed.

The process may be run at any pressure wherein the reaction proceeds.Preferable pressures are between about 14.7 and 5000 psi, morepreferably between about 50 and 1000 psi, most preferably between about100 and 300 psi.

Suitable reaction times are those which give the desired product yield.Preferable reaction times are between 30 and 300 minutes. Generallyunder suitable conditions, longer reaction times result in a greaterconversion of olefin to the hydroxymethyl-substituted product over theformyl-substituted product.

Suitable solvents for this process are polar organic solvents. Examplesof such solvents are alkanols, ethers, amides and glycol ethers.Preferred solvents are alkanols such as methanol, ethanol, propanol,butanol and the like, with ethanol being most preferred.

A by-product of this process is carbon dioxide, which can temporarilydeactivate the catalyst. It is desirable to purge the reactor withcarbon monoxide or an inert gas to remove the carbon dioxide from thereactor. It is advantageous to run this process in the absence ofoxygen-containing gases. This is done by running the reaction in acarbon monoxide, inert gas, or a mixed carbon monoxide and hydrogenatmosphere.

SPECIFIC EMBODIMENTS

The following examples are included for illustrative purposes only anddo not limit the scope of the claims or invention. Unless otherwisestated, all parts and percentages are by weight.

EXAMPLES 1-6

Procedure of Examples 1 to 6:

The reactor used for these examples is a 180 cc Aminco rocking autoclavewith a removable glass linear. In all examples, the reactor is sealedafter pressurization with carbon monoxide and the pressure is allowed tofluctuate according to temperature changes and gas consumption. Acatalyst solution is prepared by dissolving 0.19 g (0.52 mmole) of Fe₂(CO)₉ in 1.9 ml of an ethanolic potassium hydroxide (KOH) solution (0.55molar). A 0.50-ml portion of the resulting dark reddish-brown solutionis added to 0.15 ml of Fe(CO)₅ and 2.50 ml of ethanol in a glass liner.Then, 1.30 g (10 mmoles) of 3,3-diethoxypropene-1 and 0.50 ml (28mmoles) of H₂ O are added to the liner. All of the above operations arecarried out under an atmosphere of N₂. The glass liner is sealed in a180 cc rocking autoclave which is subsequently flushed with carbonmonoxide then pressurized with 210 psig of carbon monoxide. The reactionmixture is agitated by rocking while the autoclave is heated todifferent reaction temperatures and maintained at that temperature forone hour. After the reactor cools, the solution inside the liner isanalyzed by gas chromatography.

Table I describes the specific runs and the results.

                                      TABLE I                                     __________________________________________________________________________    Product Solution Composition Weight.sup.1 Percent                                                         3,3-di-       Ratio of                                     3,3-di-                                                                             3,3-di-                                                                            4,4-di-                                                                           4,4-di-                                                                           ethoxy        Linear to                                Temp                                                                              ethoxy                                                                              ethoxy                                                                             ethoxy                                                                            ethoxy                                                                            1-methyl                                                                           Con- Selec-                                                                            Branched                            Example                                                                            (° C.)                                                                     propene-1                                                                           propane                                                                            butanal                                                                           butanol                                                                           propanal                                                                           version.sup.2                                                                      tivity.sup.3                                                                      Products                            __________________________________________________________________________    1     90 96.0  --    2.8                                                                              --  0.3   4.0 78.0                                                                              10/1                                2    100 70.6  --   19.8                                                                              --  1.1  29.4 71.1                                                                              18/1                                3    110 40.1   8.8 25.0                                                                              --  1.0  59.9 43.3                                                                              25/1                                4    120 30.7  11.7 35.2                                                                              --  1.1  69.1 52.5                                                                              32/1                                5    130 11.6  17.1 39.0                                                                               5.6                                                                              1.0  88.4 51.6                                                                              37/1                                6    140  5.0  18.7 31.6                                                                              11.6                                                                              --   95.0 45.1                                    __________________________________________________________________________     .sup.1 Percentages are computed excluding the solvent.                        .sup.2 Conversion is the mole percentage of the 3,3diethoxypropene-1          consumed to product.                                                          .sup.3 Selectivity refers to the mole percentage of 4,4diethoxybutanal an     4,4diethoxybutanol in the converted product.                             

EXAMPLES 7-10

A series of examples are run in the manner described in Examples 1-6except that 3.5 ml of ethanol is used as the solvent. The examples arecarried out at 110° C., and with varied initial pressures. The resultsof these examples are described in Table II.

                                      TABLE II                                    __________________________________________________________________________                    Selectivity                                                                          3,3-diethoxy-                                               Initial    4,4-diethoxy-                                                                        1-methyl                                                                             3,3-diethoxy-                                                                        ethyl-                                        Pressure                                                                           Conversion                                                                          butanal                                                                              propanal                                                                             propane                                                                              propanoate                               Example                                                                            (psig)                                                                             (weight %)                                                                          (weight %)                                                                           (weight %)                                                                           (weight %)                                                                           (weight %)                               __________________________________________________________________________    7     50  91.2  25.5   0.8    15.9   52.6                                     8    100  70.5  47.8   4.7    20.1   22.3                                     9    200  54.9  51.4   1.0    18.0   13.1                                     10   400  10.8  73.1   3.1    --      8.3                                     __________________________________________________________________________

EXAMPLE 11

A catalyst solution is prepared by dissolving 0.15 g (0.41 mmole) of Fe₂(CO)₉ in 1.5 ml of a methanolic KOH solution (0.55 molar). A 0.50-mlportion of the resulting dark reddish-brown solution is added to 0.50 mlof Fe(CO)₅ and 2.5 ml of CH₃ OH in a glass liner. Then, 1.2 g (10mmoles) of norbornene carboxaldehyde and 0.50 ml (28 mmoles) of H₂ O areadded to the liner. All of the above operations are carried out under anatmosphere of N₂. The glass liner is sealed in a 180 cc rockingautoclave which is subsequently flushed with carbon monoxide, thenpressurized with 200 psig of carbon monoxide. The reaction mixture isagitated by rocking while the autoclave temperature is raised to 110°C., and maintained at that temperature for 50 minutes then allowed tocool. After gas chromatographic analysis, another 0.50 ml of H₂ O isadded to the liner and the liner is returned to the reactor which issealed and pressurized to 204 psig with carbon monoxide. The reactortemperature is raised to 110° C. for 45 minutes, with agitation, thenallowed to cool. After gas chromatographic analysis, the liner is againreturned to the reactor, pressurized to 200 psig with carbon monoxideand heated to 110° C., with agitation, for 45 minutes.

The results of these reactions are shown in Table III.

                                      TABLE III                                   __________________________________________________________________________    Product Solution Composition (weight %)*                                      Reaction                      Hydroxymethyl                                   Time Norbornene                                                                            Norbornene                                                                            Norbornene                                                                             Norbornene                                                                            Norbornene                              (min.)                                                                             carboxaldehyde                                                                        hydroxymethyl                                                                         dicarboxaldehyde                                                                       carboxaldehyde                                                                        dimethanol                              __________________________________________________________________________    50   62.0    4.5     21.2     3.0     2.9                                     95   44.0    6.2     28.7     8.1     5.8                                     140  33.8    6.1     30.7     12.7    7.3                                     __________________________________________________________________________     *Excluding solvent.                                                      

What is claimed is:
 1. A process for the hydroformylation of C₂₋₄alkenes, formyl-substituted C₂₋₄ alkenes, aryl-substituted alkenes,unsaturated norbornane ring-containing compounds, and α-unsaturatedacetals which comprises contacting a C₂₋₄ alkene, a formyl-substitutedC₂₋₄ alkene, aryl-substituted alkene, an unsaturated norbornanering-containing compound or an α-unsaturated acetal in a polar organicsolvent with water and carbon monoxide in the presence of a catalyticamount of a catalyst which comprises a mixture of (a) an alkali metaliron carbonyl or alkaline earth metal iron carbonyl or a mixture thereofwhich corresponds to the formula M_(a) Fe_(x) (CO)_(y) and (b) ironpentacarbonyl under conditions such that an alcohol or aldehydederivative of a C₂₋₄ alkene, a formyl-substituted C₂₋₄ alkene, anaryl-substituted alkene, unsaturated norbornane ring-containing compoundor an α-unsaturated acetal, is prepared wherein M is an alkali metal oralkaline earth metal; a is 1 or 2; x is an integer of 2 to 4, inclusive;and y is 8, 11 or
 13. 2. The process of claim 1 wherein the catalystcomprises a molar ratio of (a) an alkali metal iron carbonyl or alkalineearth metal iron carbonyl or a mixture thereof to (b) iron pentacarbonylof between about 1:0.1 and 1:10.
 3. The process of claim 2 wherein x is2 and y is
 8. 4. The process of claim 3 wherein the alkali metal ironcarbonyl is sodium iron octacarbonyl, lithium iron octacarbonyl orpotassium iron octacarbonyl.
 5. The process of claim 4 wherein thealkali metal iron carbonyl is potassium iron octacarbonyl.
 6. Theprocess of claim 4 wherein a catalytic amount of the catalyst is betweenabout 0.1 and 30 mole percent.
 7. The process of claim 6 wherein acatalytic amount of the catalyst is between about 1 and 10 mole percent.8. The process of claim 7 wherein the temperature is between about 90°C. and 140° C.
 9. The process of claim 8 wherein the pressure is betweenabout 14.7 and 5000 psi.
 10. The process of claim 9 wherein the polarorganic solvent is a glycol ether, alkanol, cyclic ether or aliphaticether.
 11. The process of claim 10 wherein the polar organic solvent isan alkanol.
 12. The process of claim 1 wherein a C₂₋₄ alkene, a C₂₋₄formyl-substituted alkene, or an aryl-substituted alkene ishydroformylated under conditions such that an alcohol or aldehydederivative or mixture thereof of the alkenes is prepared.
 13. Theprocess of claim 12 wherein the alkene corresponds to the formula

    (R.sup.1).sub.2 --C═C--(R.sup.1).sub.2

the alcohol derivative of the alkene corresponds to the formula ##STR9##and the aldehyde derivative corresponds to the formula ##STR10## whereinR¹ is separately in each occurrence hydrogen, methyl, ethyl, a formylmoiety, a phenyl group or a phenyl group substituted with an alkyl,aryl, halo, nitro, cyano, formyl, alkoxy or aryloxy group.
 14. Theprocess of claim 12 wherein the product is an alcohol derivative of thealkene.
 15. The process of claim 1 wherein an unsaturated norbornanering-containing compound is hydroformylated under conditions such that aformyl-substituted norbornane ring-containing compound, ahydroxymethyl-substituted norbornane ring-containing compound or amixture thereof is prepared.
 16. The process of claim 15 wherein theunsaturated norbornane ring-containing compound corresponds to one ofthe formulas, ##STR11## the formyl-substituted norbornanering-containing compound corresponds to one of the formulas ##STR12##and the hydroxymethyl-substituted norbornane ring-containing compoundcorresponds to one of the formulas ##STR13## wherein R² is separately ineach occurrence hydrogen, a formyl group, a hydroxymethyl or a C₁₋₂₀hydrocarbyl group, and wherein two R² 's together on adjacent carbonatoms may form a ring structure.
 17. The process of claim 16 wherein theunsaturated norbornane ring-containing compound is hydroformylated underconditions such that a hydroxymethyl-substituted norbornanering-containing compound is prepared.
 18. The process of claim 17wherein an unsaturated norbornane ring-containing compound with one R²which a formyl substituent and the remaining R² 's are hydrogen, ishydroformylated under conditions such that a dihydroxymethyl norbornanering-containing compound is prepared.
 19. The process of claim 1 whereinan α-unsaturated acetal is hydroformylated under conditions such that aformyl-substituted acetal, hydroxymethyl-substituted acetal or a mixturethereof is prepared.
 20. The process of claim 19 wherein theα-unsaturated acetal corresponds to the formula ##STR14## theformyl-substituted acetal corresponds to the formula ##STR15## and thehydroxymethyl-substituted acetal corresponds to the formula ##STR16##wherein R³ is hydrogen or C₁₋₂₀ alkyl; R⁴ is hydrogen or methyl; and R⁵is C₁₋₂₀ hydrocarbyl; or both R⁵ 's may combine to form a cyclic acetalring.
 21. The process of claim 20 wherein the α-unsaturated acetal ishydroformylated under conditions such that a hydroxymethyl-substitutedacetal is prepared.